WO2020227485A1 - Curable fluoroelastomer compositions - Google Patents
Curable fluoroelastomer compositions Download PDFInfo
- Publication number
- WO2020227485A1 WO2020227485A1 PCT/US2020/031801 US2020031801W WO2020227485A1 WO 2020227485 A1 WO2020227485 A1 WO 2020227485A1 US 2020031801 W US2020031801 W US 2020031801W WO 2020227485 A1 WO2020227485 A1 WO 2020227485A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dihydrazide
- fluoroelastomer composition
- curable fluoroelastomer
- curable
- perfluoro
- Prior art date
Links
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 119
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 17
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims description 14
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 claims description 12
- QSBINWBNXWAVAK-PSXMRANNSA-N PE-NMe(16:0/16:0) Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP(O)(=O)OCCNC)OC(=O)CCCCCCCCCCCCCCC QSBINWBNXWAVAK-PSXMRANNSA-N 0.000 claims description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical group FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- DMUPYMORYHFFCT-UPHRSURJSA-N (z)-1,2,3,3,3-pentafluoroprop-1-ene Chemical compound F\C=C(/F)C(F)(F)F DMUPYMORYHFFCT-UPHRSURJSA-N 0.000 claims description 3
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 claims description 3
- WUMVZXWBOFOYAW-UHFFFAOYSA-N 1,2,3,3,4,4,4-heptafluoro-1-(1,2,3,3,4,4,4-heptafluorobut-1-enoxy)but-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)F WUMVZXWBOFOYAW-UHFFFAOYSA-N 0.000 claims description 3
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims description 3
- LYIPDZSLYLDLCU-UHFFFAOYSA-N 2,2,3,3-tetrafluoro-3-[1,1,1,2,3,3-hexafluoro-3-(1,2,2-trifluoroethenoxy)propan-2-yl]oxypropanenitrile Chemical compound FC(F)=C(F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C#N LYIPDZSLYLDLCU-UHFFFAOYSA-N 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 229920002313 fluoropolymer Polymers 0.000 claims description 3
- 239000004811 fluoropolymer Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- RLUQVTMWPIHWLE-UHFFFAOYSA-N 1,3-diaminourea;dihydrochloride Chemical compound Cl.Cl.NNC(=O)NN RLUQVTMWPIHWLE-UHFFFAOYSA-N 0.000 claims description 2
- GFQJOAYQSOWWOE-UHFFFAOYSA-N 1-amino-3-(hydrazinecarbonyl)urea Chemical compound NNC(=O)NC(=O)NN GFQJOAYQSOWWOE-UHFFFAOYSA-N 0.000 claims description 2
- XKKJWUZFAQPKQO-UHFFFAOYSA-N 3-[3-(2-carboxyethyl)imidazolidin-1-yl]propanoic acid Chemical compound OC(=O)CCN1CCN(CCC(O)=O)C1 XKKJWUZFAQPKQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 229960000250 adipic acid Drugs 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 2
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- PSIKPHJLTVSQFO-UHFFFAOYSA-N propanedihydrazide Chemical compound NNC(=O)CC(=O)NN PSIKPHJLTVSQFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 4
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- BGEVFSCRPUOYHH-UHFFFAOYSA-N 1-amino-3-(hydrazinecarbonylamino)urea Chemical compound NNC(=O)NNC(=O)NN BGEVFSCRPUOYHH-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 28
- 230000008569 process Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 235000019241 carbon black Nutrition 0.000 description 13
- 150000002170 ethers Chemical class 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- -1 diamine compounds Chemical class 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 150000002825 nitriles Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000005829 chemical entities Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 3
- WBLRBQCSSBJIPF-UHFFFAOYSA-N 3-bromo-1,1,2,3-tetrafluorobut-1-ene Chemical compound CC(F)(Br)C(F)=C(F)F WBLRBQCSSBJIPF-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000006244 Medium Thermal Substances 0.000 description 3
- 229920006169 Perfluoroelastomer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101100273965 Solanum lycopersicum HCR9-0 gene Proteins 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SPFPGSYLNIIQMG-UHFFFAOYSA-N (carboxyamino)carbamic acid Chemical compound OC(=O)NNC(O)=O SPFPGSYLNIIQMG-UHFFFAOYSA-N 0.000 description 1
- LYFDLKBUDYFSTI-UHFFFAOYSA-N 1-[difluoro(trifluoromethoxy)methoxy]-1,1,2,2-tetrafluoro-2-(1,2,2-trifluoroethenoxy)ethane Chemical group FC(F)=C(F)OC(F)(F)C(F)(F)OC(F)(F)OC(F)(F)F LYFDLKBUDYFSTI-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical class FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- GQILCMONWYJNFP-UHFFFAOYSA-N 4-[2-(3-amino-4-anilinophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-1-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC(C(C=2C=C(N)C(NC=3C=CC=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=CC=C1NC1=CC=CC=C1 GQILCMONWYJNFP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- KEACLAVDTZRACA-UHFFFAOYSA-N [4-(2-carbamoylhydrazinyl)anilino]urea Chemical compound NC(=O)NNC1=CC=C(NNC(N)=O)C=C1 KEACLAVDTZRACA-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
Definitions
- curable fluoroelastomer compositions and, more particularly, curable fluoroelastomer compositions comprising a mixture of two or more dihydrazide curing agents.
- Fluoroelastomers have achieved outstanding commercial success and are used in a wide variety of applications in which severe environments are encountered, in particular those end uses where exposure to high temperatures and aggressive chemicals occurs.
- these polymers are often used as down-well drill bit seals in the oil and gas industry where the drilling assembly is exposed to aqueous environments at high temperatures and pressures followed by rapid return to atmospheric pressure.
- seals there is a constant need for seals for use in these extreme environments which exhibit a desirable combination of low temperature sealing performance in combination with rapid gas decompression resistance and hot water resistance.
- fluoroelastomers are largely attributable to the stability and inertness of the copolymerized fluorinated monomer units that make up the major portion of the polymer backbones in these compositions.
- Such monomers include vinylidene fluoride, hexafluoropropylene,
- fluoroelastomers are typically crosslinked, i.e., vulcanized or cured. To this end, a small percentage of cure site monomer is copolymerized with the fluorinated monomer units. Cure site monomers containing at least one nitrile group, for example perfluoro-8-cyano-5-methyl-3,6- dioxa-1 -octene, are especially preferred. The cure sites cross-link the
- fluoropolymers by reacting with one or more curatives, for example diamine compounds, bisphenol compounds, and peroxide compounds.
- curatives for example diamine compounds, bisphenol compounds, and peroxide compounds.
- nitrogen-containing nucleophilic compounds have been employed to crosslink fluoroelastomers having nitrile group cure sites. See, for example, U.S. Patent No. 6,638,999 B2. Some of these curatives are scorchy (i.e., crosslinking may begin before the final shaping of the composition), while others are volatile at rubber milling temperatures.
- the cured compositions can exhibit improved physical properties, especially for use in the oil and gas industry in down-hole applications.
- a curable fluoroelastomer composition including at least one fluoroelastomer comprising copolymerized units of a nitrile group-containing cure site monomer; a cure system comprising at least two different dihydrazides; and optionally at least one additive. Further provided are methods of curing the fluoroelastomer composition, pre-forms comprising the curable fluoroelastomer composition, cured fluoroelastomer compositions that are the product of cross-linking the curable fluoroelastomer composition, and articles comprising the cured fluoroelastomer compositions. DETAILED DESCRIPTION OF THE INVENTION
- phr refers to parts per hundred parts of fluoroelastomer (rubber); one of skill in the art uses and recognizes this term of measurement. For example, 3 parts of a component per 100 parts fluoroelastomer is written as 3 phr. In the compounds, processes, and articles described herein, phr is based on 100 parts of fluoroelastomer A.
- t90 refers to the time in minutes required for the torque to reach 90 % of its maximum at a given temperature when a force is applied to a curable
- fluoroelastomer composition as measured by a moving die rheometer or similar instrument.
- mole percent refers to mole percent
- compositions that include greater than 95 weight % or greater than 99 weight % of the recited component(s), based on the total weight of the composition.
- compositions to which this term is applied may include one or more other components or additives such those described below, including any carrier(s) that may be introduced with the other
- component(s) or additive(s) In these amounts, the other component(s), the additive(s) and their carrier(s) do not change the basic and novel characteristics of the phases or compositions described herein.
- compositions, a process, a structure, or a portion of a composition, a process, or a structure is described herein using an open-ended term such as “comprising,” unless otherwise stated the description also includes an
- compositions, processes or structures described herein may be employed in connection with various elements and components of compositions, processes or structures described herein. This is merely for convenience and to give a general sense of the compositions, processes or structures. Such a description includes“one or at least one” of the elements or components. Moreover, as used herein, the singular articles also include a description of a plurality of elements or
- the conjunction “or” refers to an inclusive or and not to an exclusive or.
- the condition“A or B” is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
- Exclusive“or” is designated herein by terms such as “either A or B” and“one of A or B”, for example.
- ranges set forth herein include their endpoints unless expressly stated otherwise in limited circumstances. Further, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether such pairs are separately disclosed. The scope of the invention is not limited to the specific values recited when defining a range, but rather includes every real number within the range, inclusive of its endpoints.
- any description of a variant of materials, chemical entities, methods, steps, values, ranges, etc., whether identified as preferred or not, of the processes, compounds and articles described herein specifically includes the combination of the variant with the other materials, methods, steps, values, ranges, etc., that make up or form the processes, compounds and articles described herein.
- perfluoro refers to a molecule or moiety in which every hydrogen atom is substituted with a fluorine atom.
- perfluorinated olefin refers to linear, branched, or cyclic structures which comprise at least one unsaturated double bond and which comprise fluorine atoms and carbon atoms, but no hydrogen atoms.
- the prefix“fluoro-” when preceding a chemical entity name, indicates both“fluoro-” entities and“perfluoro-” entities.
- alkyl refers to linear, branched, or cyclic hydrocarbon structures and combinations of two or more of these structures.
- alkyl does not include unsaturated or aromatic structures.
- linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.
- Branched alkyl groups include for example sec-butyl, fe/f-butyl, and isopropyl groups.
- cyclic hydrocarbon groups include cyclopropyl, cyclopentyl, cyclohexyl, cyclobutyl, and cyclooctyl groups.
- alkoxy or“alkoxyl” refers to alkyl groups attached to an oxygen atom by a single bond. The other bond of the oxygen atom is connected to a carbon atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, cyclopropyloxy, cyclopentyloxy, and cyclohexyloxy.
- curable as used herein whether alone or in combined form, such as“cured”,“curing”, or“curable”, is synonymous and used interchangeably with the terms“cross-link” and“vulcanize” to refer to polymers that comprise reactive moieties, wherein said reactive moieties have been reacted to form covalent bonds, at least a portion of which are covalent bonds between two polymer molecules.
- the curable fluoroelastomer composition described herein may be cured to form sufficient crosslinks such that the resultant cured fluoroelastomer composition cannot be thermally processed, for example, molded or extruded. That is, when the curable fluoroelastomer composition is exposed to curing conditions, for example in a compression-molding process, and has thereby been cured to form an article, that article cannot be re-molded to take on a
- the cured fluoroelastomer compositions are thermoset materials.
- the resultant entity of the curing process is a“cured” entity, that is, a bulk fluoroelastomer or an article as defined herein above. Curing results in
- Cured articles of compounds described herein include, but are not limited to, blocks, slabs, O-rings, seals, and gaskets.
- curable also expressly includes differing degrees of cross-linking a curable composition, such as by controlling the stoichiometry of curing sites or cross-linking agents, or by controlling curing conditions, such as time,
- the curable fluoroelastomer compositions described herein may be partially cross-linked, completely cross-linked, or substantially completely cross- linked, depending on the desired properties of the cured fluoroelastomer compositions or articles.
- the cured fluoroelastomer compositions or the articles comprising the cured fluoroelastomer compositions may also be“post-cured”, that is, subjected to additional curing conditions, which provide further, subsequent curing.
- Curable compositions that have undergone more than one curing cycle i.e. , “post-cured” compositions, may also be referred to as“cured.”
- the curable fluoroelastomer compositions described herein comprise at least one fluoroelastomer having nitrile group cure sites and a cure system comprising at least two different dihydrazide curing agents.
- the curable fluoroelastomer compositions comprise:
- the curable fluoroelastomers preferably contain between 25 and
- first monomers include but are not limited to 1 ,1 -difluoroethylene
- C 2 H 2 F 2 hexafluoro-propylene (HFP), tetrafluoroethylene (TFE), 1 , 2, 3,3,3- pentafluoropropene (1 -HPFP), 1 ,1 ,3,3,3-pentafluoropropene (2-FIPFP), chlorotrifluoroethylene (CTFE), 1 ,1 ,2-trifluoro-ethylene, 1 -fluoroethylene, and combinations of two or more of these first monomers.
- HFP hexafluoro-propylene
- TFE tetrafluoroethylene
- 1 -HPFP 1, 3,3,3- pentafluoropropene
- 2-FIPFP 1 ,1 ,3,3,3-pentafluoropropene
- CTFE chlorotrifluoroethylene
- fluoroelastomer further comprises copolymerized residues of a second monomer that is a fluorovinyl ether and copolymerized units of a cure site monomer.
- curable fluoroelastomer (A) may further comprise copolymerized units of one or more additional copolymerized monomers, different from said first monomer, said second monomer, and said cure site monomer.
- Suitable fluorine-containing vinyl ethers for use as monomer (ii) to make fluoroelastomers include but are not limited to fluoro(alkyl vinyl) ethers. Preferred are perfluoro(alkyl vinyl) ethers (PAVE). Suitable perfluoro(alkyl vinyl) ethers for use as monomers include those of the formula
- CF 2 CFO(RrO)n(RrO)mRf (I) where R r and R r, are different linear or branched perfluoroalkylene groups of 2 to 6 carbon atoms; m and n are integers independently selected from the range of 0 to 10; and R f is a perfluoroalkyl group of 1 to 6 carbon atoms.
- a preferred class of perfluoro(alkyl vinyl) ethers includes compositions of the formula
- CF 2 CFO(CF 2 CFXO)nRf (II) where X is F or CF3; n is an integer in the range of 0 to 5; and Rf is a
- perfluoroalkyl group of 1 to 6 carbon atoms A more preferred class of perfluoro(alkyl vinyl) ethers includes
- CF30-(CF 2 0)n-CF 2 CF2-0CF CF2 (III) where n is an integer in the range of 0 to 5.
- n is an integer in the range of 0 to 5.
- An example of a more preferred perfluorinated ether is 1-[2-[difluoro(trifluoromethoxy) methoxy]-1 ,1 ,2,2- tetrafluoroethoxy]-1 ,2,2-trifluoroethene.
- a still more preferred class of perfluoro(alkyl vinyl) ethers includes those ethers wherein n is 0 or 1 and R f contains 1 , 2, or 3 carbon atoms.
- Examples of such perfluorinated ethers include, without limitation, perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE), and perfluoro(propyl vinyl) ether (PPVE).
- CF 2 CF0[(CF 2 CF ⁇ CF 3 ⁇ 0) n (CF 2 CF 2 CF 2 0) m (CF 2 )p]CxF 2x+1 (V)
- the content of copolymerized PAVE units generally ranges from 25 to 75 weight percent, preferably from 35 to 65 weight percent, based on the total weight of the curable fluoroelastomer.
- the curable fluoroelastomer preferably contains between 40 and 60 wt% of copolymerized PMVE units.
- the curable fluoroelastomer further contains nitrile group-containing cure site monomers, generally in amounts of from 0.1 to 5 weight percent. The range is preferably between 0.5 to 3.5 weight percent and more preferably from 1 to 3 weight percent, based on the total weight of the curable fluoroelastomer.
- Suitable cure site monomers include nitrile-containing perfluorinated olefins and nitrile-containing perfluorinated vinyl ethers.
- Useful nitrile-containing cure site monomers include those of the formulas shown below.
- CF2 CF-0(CF2)n-CN (VII) where n is is selected from the range of 2 to 12, preferably from the range of 2 to 6;
- CF2 CF-0[CF2-CFCF 3 -0]n-CF2-CFCF 3 -CN (VIII) where n is 0, 1 , 2, 3, or 4, preferably 0, 1 , or 2;
- CF2 CF-[0CF 2 CFCF 3 ] x -0-(CF2)n-CN (IX) where x is 1 or 2, and n is 1 , 2, 3, or 4; and
- CF2 CF-0-(CF 2 )n-0-CF(CF 3 )CN (X) where n is 2, 3, or 4.
- Nitrile-containing perfluorinated vinyl ethers of formula (VIII) are preferred. More preferred cure site monomers are perfluorinated polyethers having a nitrile group and a trifluorovinyl ether group. A still more preferred cure site monomer is
- CF2 CF0CF2CF(CF 3 )0CF 2 CF 2 CN
- XI perfluoro(8-cyano-5-methyl-3,6-dioxa-1 -octene) or 8-CNVE.
- Suitable optional additional monomers include, without limitation, hydrocarbon olefins. Suitable hydrocarbon olefins include but are not limited to ethylene and propylene. Cure site monomers that do not comprise nitrile groups, such as for example the isomers of trifluoropropylene (TFP) and the isomers of bromotetrafluorobutene (BTFB), are also suitable additional monomers. When copolymerized units of a hydrocarbon olefin are present in the curable
- fluoroelastomers they are present at a level of 0.1 to 30 wt%, or 4 to 30 wt%, or 0.1 to 25 wt%, 0.1 to 20 wt%, 0.1 to 15 wt%, 0.1 to 10 wt%, or 0.1 to 5 wt%, based on the total weight of the curable fluoroelastomer.
- One suitable curable fluoroelastomer that comprises an optional additional monomer is
- curable fluoroelastomer (A) comprises copolymerized units of: i) at least one first monomer which is a perfluorinated olefin; ii) at least one second monomer which is a perfluorovinyl ether; and iii) one or more nitrile group-containing cure site monomers selected from the group consisting of nitrile-containing perfluorinated olefins and nitrile-containing perfluorinated vinyl ethers.
- the amounts of the copolymerized residues of all the comonomers in the curable fluoroelastomer are complementary. Stated alternatively, the sum of the weight percentages of the copolymerized residues of all the comonomers in the curable fluoroelastomer is 100 wt%.
- Suitable fluoroelastomers may be prepared by methods that are known in the art, for example those described in U.S. Patent No. 5,789,489.
- the cure system used in the curable fluoroelastomer compositions comprises a curative mixture of at least two different dihydrazides. Suitable dihydrazides are described in U.S. Patent Nos. 8,765,875 and 8,765,876, both issued to Bish et al.
- Preferred dihydrazides include, without limitation, malonic dihydrazide; succinic dihydrazide; adipic dihydrazide; oxalyl dihydrazide; 1 ,3- imidazolidinedipropanoic acid, 4-(1 -methylethyl)-2,5-dioxo-, 1 ,3-dihydrazide; tetradecanedioic acid, 1 ,14-dihydrazide; hexanedioic acid, 2, 2, 3, 3, 4, 4, 5, 5- octafluoro-, 1 ,6-dihydrazide; isophthalic dihydrazide; carbonic dihydrazide;
- dihydrazide diaminobiuret; and p-phenylene-bis-semicarbazide. More preferred dihydrazides include isophthalic dihydrazide and oxalyl dihydrazide.
- dihydrazides are chosen to balance or optimize the properties of the cured fluoroelastomers.
- a dihydrazide curative that acts upon a fluoroelastomer composition to produce a cured fluoroelastomer having given hardness and given elongation at break may be combined with a second, different dihydrazide curative that acts upon the same fluoroelastomer to produce a cured fluoroelastomer having a similar hardness and a different elongation at break.
- the cured fluoroelastomer resulting from the combination of dihydrazides acting upon the same fluoroelastomer composition may have an elongation at break that is intermediate between those of the cured fluoroelastomers that were produced from the individual dihydrazides.
- Curative mixtures of two different dihydrazides are preferred.
- the two dihydrazides may be combined in a weight ratio of from about 99:1 to about 1 :99; from about 49:1 to about 1 :49; from about 19:1 to about 1 :19; from about 9:1 to about 1 :9; from about 5:1 to about 1 :5; from about 4:1 to about 1 :4; or from about 3:1 to about 1 :3.
- a weight ratio of about 3:1 to about 1 :2 is preferred.
- the two different dihydrazides are isophthalic dihydrazide and oxalyl dihydrazide in a weight ratio of isophthalic dihydrazide:oxalyl dihydrazide ranging from about 3: 1 to about 1 :2 or from about 1 : 1 to about 2:1.
- a curative accelerator e.g. a compound that releases ammonia at curing temperatures
- dihydrazide curatives examples include but are described in U.S. Patent No.
- fluoroelastomers having nitrile-group cure sites may be used in addition to the dihydrazides.
- examples of such other curatives include, but are not limited to, diaminobisphenol AF, 2,2-bis(3-amino-4-anilinophenyl)hexafluoropropane, mono- or bis-amidines, mono- or bis-amidrazones, mono- or bis-amidoximes, or an organic peroxide plus coagent.
- the total concentration of the cure system in the fluoroelastomer composition may range from about 0.1 to about 4 phr, preferably from about 0.5 to 2 phr.
- a composition comprising 100 parts by weight of fluoroelastomer may further comprise 0.5 phr of oxalyl dihydrazide and 0.8 phr of isophthalic dihydrazide for a total of 1.3 phr of cure system per 100 phr and a ratio of 1.6:1 of the weight of isophthalic dihydrazide to the weight of oxalyl dihydrazide.
- Optional additives that may be used in the fluoroelastomer compositions to improve or optimize various physical properties include, without limitation, carbon blacks, fluoropolymer micropowders, stabilizers, plasticizers, lubricants, fillers (e.g., mineral fillers such as silicas, alumina, aluminum silicate, barium sulfate, titanium dioxide), co-agents, and processing aids.
- Suitable optional additives have sufficient thermal, chemical, or mechanical stability to be incorporated into the curable fluoroelastomer compositions under their processing conditions, including curing conditions, or to perform satisfactorily under the cured
- fluoroelastomer compositions intended service conditions.
- suitable carbon blacks include carbon blacks having particle sizes ranging from about 10 nm (small) to 500 nm (large).
- An example of small particle size carbon blacks include SAF carbon black, Spheron 6400® and FEF carbon, a highly reinforcing black with typical average particle size of about 14 nm and designated N 110 in Group No. 1 , according to ASTM D 1765.
- a larger carbon black particle as discussed in U.S. Pat. No. 5,554,680, describes a particular class of carbon blacks that have average particle sizes of at least about 100 nm to about 500 nm as determined by ASTM D 3849.
- Examples include MT blacks (medium thermal black) designated N-991 , N-990, N-908, and N-907, and large particle size furnace blacks, of which MT blacks are preferred. Blends of small and large particle size carbon blacks may also be used.
- the larger carbon black particle in a blend of carbon black particles of different particle sizes may be present in an amount ranging from about 40 to 60 phr, and the smaller carbon black particle may be in the range of from 2 to 8 phr.
- the total concentration of the optional additive(s) may range from about 0.1 to 200 phr, preferably from about 1 to 100 phr.
- the curable fluoroelastomer compositions may be prepared by mixing the fluoroelastomer, cure system, and optional additives using standard rubber compounding procedures.
- the components may be mixed on a two-roll rubber mill, in an internal mixer (e.g. a BanburyTM internal mixer), or in an extruder.
- the curable fluoroelastomer compositions may be formed into objects of various shapes by physical means, without undergoing any chemical reaction. These uncured objects are known as“pre-forms”.
- the curable compositions may be shaped into pre-forms by any suitable method, such as rolling, molding, die cutting, or extrusion, for example.
- the pre-forms may be subjected to curing conditions, such as heat or pressure, to form cured articles.
- the curable fluoroelastomer compositions may be formed into blanks having the shape of discs, slabs, or blocks, for example.
- the blank may have no set form, if it is cured in the same form in which the curable composition is produced or compounded. The blanks are cured and then machined to form articles comprising the cured fluoroelastomer composition.
- the shape and size of the curable composition, before curing, is determined by the dimensions of the machined article.
- the cured article or blank may be similar in shape and size to the pre-form or uncured blank from which it is produced, although the dimensions may vary between the two.
- the curable fluoroelastomer composition may be shaped and crosslinked (i.e. , cured) by application of heat, pressure, or both heat and pressure to produce a cured article. Molding is generally followed by a post cure cycle during which the press cured composition is heated at an elevated temperature, for example in excess of 300°C, for several hours.
- a press cure cycle is preferably also used.
- the cured fluoroelastomer compositions have excellent thermal stability, sealing properties, and hot water resistance, and a favorable balance of other properties, including elongation at break, modulus, hardness, compression set, and volume swell.
- the cured fluoroelastomer compositions and the blanks and articles comprising the cured fluoroelastomer compositions have a volume swell, measured according to ASTM D1414:2015 after exposure to 225°C water for 70 hours, of less than 5%, 8%, 10% or 20%; or an elongation at break, measured according to ASTM D412-06a:2013, of at least 40%, 43%, 46%, 50%, 60%, 70%, 80%, 90%, or 100%.
- the curable fluoroelastomer compositions are useful in the production of gaskets, tubing, and seals, for example.
- Cured articles produced from the curable fluoroelastomer compositions are particularly useful in the oil and gas industry for down-well applications, where the drilling assembly may be exposed to aqueous environments at high temperatures and where the pressures may fluctuate rapidly.
- FFKM A perfluoroelastomer containing 61.9 mole percent of copolymerized units of TFE, 37.4 mole percent of copolymerized units of PMVE, and 0.7 mole percent of copolymerized units of 8-CNVE was prepared according to the general processes described in U.S. Patent Nos. 5,789,489; 7,977,426; and 7,999,049.
- Oxalyl dihydrazide (CAS # 996-98-5) was obtained from Sigma-Aldrich, St.
- Isophthalic dihydrazide (CAS # 2760-98-7) was obtained from TCI America, Portland, Oregon, USA.
- Carbon Black a thermal carbon black having an average particle size of 280 nm, available as ThermaxTM N990 from Cancarb of Medicine Flat, Alberta, Canada.
- Plasticizer A perfluoropolyether available from The Chemours Company FC,
- Modulus, elongation at break, and tensile strength at break were determined according to ASTM D412-06a:2013.
- Dumbbell shaped test samples (Fig. 2 ASTM D 412-06a Vol. 09-01 , die“C”) were cut from 2 mm (0.8”) thick molded and cured slabs of fluoroelastomer composition. Test samples were conditioned for 3 hours prior to testing at 23 °C and 50 % relative humidity.
- Shore A hardness was determined according to ASTM D2240- 05:2010.
- Dumbbell shaped test samples (Fig. 2 ASTM D 412-06a Vol. 09-01 , die “C”) were cut from molded and cured slabs of fluoroelastomer composition. Test samples were conditioned for 3 hours prior to testing at 23 °C and 50 % relative humidity before testing.
- Compression set at constant deflection (25%) was determined according to ASTM D395-14:2014.
- the sample type was AS-214 O-rings, from which a small section of each O-ring was cut and removed to allow the inside surfaces to be exposed to the same environment as the outside surfaces.
- three AS-214 O-ring samples were compressed and aged at elevated temperature in air or water. After aging, the samples were removed from their compression apparatus, allowed to cool to room temperature, and measured in height to determine the relationship of their original height prior to compression and aging (ho) to their height after compression and aging (h), expressed as the percentage (h/ho)*100. The median of three results for each composition was reported in the tables. Volume Percent Swell
- volume percent swell was measured according to ASTM D471 -12a:2012 on AS-214 O-rings. Before testing, O-rings are weighed in air and in an ethanol/water solution having a specific gravity of 0.820+/-0.001 at 23 °C. The 0- rings were then aged in distilled water at 225°C for 70 hours using the aging procedure in ASTM D1414:2015. After aging in distilled water, the O-rings were reweighed in air and the ethanol/water solution to determine percent volume swell. The change in volume was calculated using Archimedes’ Principle whereby the density of an article can be determined by obtaining the weight of the article in air and the weight of that article in a fluid of known density. Volume percent swell after aging was calculated in accordance the equation in D471 - 12a:2012 Section 17.2 (3).
- Curable fluoroelastomer compositions were compounded on a two-roll rubber mill with the components and in the proportions shown in Tables 1 and 2. O-rings for compression set and volume swell testing were made from these curable fluoroelastomer compositions by press curing at a temperature of 200 °C for a time period to reach t90 plus 5 minutes, followed by a post cure in a nitrogen atmosphere at a temperature of 305°C for 26 hours. Physical properties of the cured fluoroelastomer compositions are shown in Tables 1 and 2.
- Table 1 shows the properties of the cured fluoroelastomer composition E1 which comprises a mixture of dihydrazides compared to the properties of fluoroelastomer compositions C1 and C2, which comprise only a single dihydrazide as the curing agent.
- E1 contains about half the mass of each dihydrazide respectively. Based on this relationship, it was expected that properties dependent on the cure site structure such as volume swell for E1 would be approximately average between those of the C1 and C2 formulations. However, the measured volume swell of E1 is considerably less than the expected average volume swell based on C1 and C2. Therefore, the measured volume swell of E1 compared to those of C1 and C2 is unexpectedly small, while the balance of other favorable properties such as elongation is maintained.
- Table 2 shows the properties of the cured fluoroelastomer composition E2, which comprises a mixture of dihydrazides in a different ratio of isophthalic dihydrazide to oxalyl dihydrazide, compared to the properties of fluoroelastomer compositions C3 and C4, which comprise only a single dihydrazide as the curing agent.
- the volume swell of E2 is considerably less than the expected volume swell based on C3 and C4. Therefore, the measured volume swell of E2 compared to those of C3 and C4 is unexpectedly small, while the balance of other favorable properties such as elongation is maintained.
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4281092A (en) | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
US4394489A (en) | 1982-02-25 | 1983-07-19 | E. I. Du Pont De Nemours & Co. | Fluoroelastomer curatives |
US5554680A (en) | 1994-02-16 | 1996-09-10 | E. I. Du Pont De Nemours And Company | Heat-resistant perfluoroelastomer composition |
US5789509A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Perflouroelastomer composition having improved processability |
US5789489A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
EP0863941A2 (en) * | 1995-12-01 | 1998-09-16 | E.I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
US6281296B1 (en) | 1998-08-10 | 2001-08-28 | Dupont Dow Elastomers L.L.C. | Curable perfluoroelastomer composition |
US6638999B2 (en) | 2000-02-08 | 2003-10-28 | Dupont Dow Elastomers Llc. | Curable perfluoroelastomer composition |
US20110095969A1 (en) | 2007-08-08 | 2011-04-28 | Takashi Ueda | Liquid crystal display device and production thereof |
US7977426B2 (en) | 2008-11-13 | 2011-07-12 | E. I. Du Pont De Nemours And Company | Fluoroalkyl ether sulfonate surfactants |
WO2011084404A2 (en) | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Peroxide cured partially fluorinated elastomers |
US7999049B2 (en) | 2008-01-22 | 2011-08-16 | Dupont Performance Elastomers L.L.C. | Process for producing fluoroelastomers |
US8765875B2 (en) | 2011-03-31 | 2014-07-01 | E I Du Pont De Nemours And Company | Curable fluoroelastomer composition |
WO2017132706A1 (en) * | 2016-01-26 | 2017-08-03 | E I Du Pont De Nemours And Company | Fluoroelastomer compounds |
WO2018038917A1 (en) * | 2016-08-25 | 2018-03-01 | E. I. Du Pont De Nemours And Company | Fluoroelastomer compounds |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2940298B1 (en) * | 2008-12-23 | 2012-07-13 | Michelin Soc Tech | COMPOSITION BASED ON NATURAL RUBBER AND INORGANIC REINFORCING LOAD COMPRISING DIHYDRAZIDE. |
US9169339B2 (en) * | 2010-12-07 | 2015-10-27 | Daikin Industries, Ltd. | Curable composition, molded product and method for producing molded product |
FR2969165B1 (en) * | 2010-12-21 | 2014-06-06 | Michelin Soc Tech | COMPOSITION BASED ON NATURAL RUBBER AND CARBON BLACK COMPRISING HYDRAZIDE, HYDRAZONE OR POLYAMINO |
US8338542B1 (en) * | 2012-06-25 | 2012-12-25 | E I Du Pont De Nemours And Company | Curable fluoroelastomer composition |
CN108473718B (en) * | 2015-10-29 | 2021-03-30 | 纳幕尔杜邦公司 | Curable fluoroelastomer compositions |
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Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4281092A (en) | 1978-11-30 | 1981-07-28 | E. I. Du Pont De Nemours And Company | Vulcanizable fluorinated copolymers |
US4394489A (en) | 1982-02-25 | 1983-07-19 | E. I. Du Pont De Nemours & Co. | Fluoroelastomer curatives |
US5554680A (en) | 1994-02-16 | 1996-09-10 | E. I. Du Pont De Nemours And Company | Heat-resistant perfluoroelastomer composition |
EP0863941A2 (en) * | 1995-12-01 | 1998-09-16 | E.I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
US5789509A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Perflouroelastomer composition having improved processability |
US5789489A (en) | 1996-11-25 | 1998-08-04 | E. I. Du Pont De Nemours And Company | Fast-curing perfluoroelastomer composition |
US6281296B1 (en) | 1998-08-10 | 2001-08-28 | Dupont Dow Elastomers L.L.C. | Curable perfluoroelastomer composition |
US6638999B2 (en) | 2000-02-08 | 2003-10-28 | Dupont Dow Elastomers Llc. | Curable perfluoroelastomer composition |
US20110095969A1 (en) | 2007-08-08 | 2011-04-28 | Takashi Ueda | Liquid crystal display device and production thereof |
US7999049B2 (en) | 2008-01-22 | 2011-08-16 | Dupont Performance Elastomers L.L.C. | Process for producing fluoroelastomers |
US7977426B2 (en) | 2008-11-13 | 2011-07-12 | E. I. Du Pont De Nemours And Company | Fluoroalkyl ether sulfonate surfactants |
WO2011084404A2 (en) | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Peroxide cured partially fluorinated elastomers |
US8765875B2 (en) | 2011-03-31 | 2014-07-01 | E I Du Pont De Nemours And Company | Curable fluoroelastomer composition |
US8765876B2 (en) | 2011-03-31 | 2014-07-01 | E I Du Pont De Nemours And Company | Curable fluoroelastomer composition |
WO2017132706A1 (en) * | 2016-01-26 | 2017-08-03 | E I Du Pont De Nemours And Company | Fluoroelastomer compounds |
WO2018038917A1 (en) * | 2016-08-25 | 2018-03-01 | E. I. Du Pont De Nemours And Company | Fluoroelastomer compounds |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 2760-98-7 |
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JP2022532325A (en) | 2022-07-14 |
CN114127160B (en) | 2023-08-15 |
US20220306782A1 (en) | 2022-09-29 |
KR20220005569A (en) | 2022-01-13 |
EP3966279A1 (en) | 2022-03-16 |
CN114127160A (en) | 2022-03-01 |
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